Process for polymerization of cycloolefins and polymerizable cycloolefins

ABSTRACT

Process for the catalytic copolymerisation (ROMP) of strained activated cyclic olefins comprising contacting an activated strained mono (poly)cyclic olefin monomer of formula                    
     with at least 1 wt % of an activated strained di (poly)cyclic olefin monomer of formula                    
     in the presence of a catalyst or an initiating agent wherein the group                    
     represents a strained (poly)cyclic olefin, tail Y and spacer X comprise preferably electron withdrawing and property modulating groups 
     whereby the monomers form a copolymer comprising the repeating unit                    
     and at least 1 wt % of the unit                    
     which is adapted for subsequent cross linking of respective copolymer chains in the presence of heat and catalyst to form an amount of a cross linked copolymer comprising the unit,                    
     and polymeric products obtained thereby, novel monomers and intermediates, a method for selecting monomers for reaction a method for the preparation of shaped products by RIM or RTM, and shaped products obtained thereby.

This is a nationalization of PCT/GB00/02548 filed Jul. 10, 2000 andpublished in English.

The present invention relates to a process for the polymerisation ofolefins, novel polymerisable olefins, curable compositions thereof, theproducts thereof and their use in the preparation of shaped products,coatings and the like. More particularly the invention relates to aprocess for the copolymerisation of monofunctional and bifunctionalstrained bicyclic olefin monomers, novel monofunctional and bifunctionalstrained bicyclic olefin monomers, and their associated compositions,products and uses.

The polymerisation of dicyclopentadiene (DCPD) has long been known andcommercially operated for the production of shaped thermoset crosslinked products which are extremely bard. The products are particularlyuseful since they undergo surface oxidation allowing them to be painted,and rendering them odorless. The catalysts employed are air sensitiveand functional group sensitive, complicating the process, and limitingthe reaction in terms of monomer variation.

Polymerisation of derivatives is known from the literature. Inparticular a number of publications (Ciba Geigy) relate to novel(“Grubbs”) catalysts for use in polymerising strained olefins and theirderivatives. The catalysts are disclosed as suited for thepolymerisation of a vast range of polymerisable monofunctional monomersand difunctional bridged monomers, by virtue of their excellent moisturetolerance. However polymerisation of only a limited number of thedisclosed monomer and dimer classes is described. WO 97/38036 describesring opening metathesis polymerisation of an at least 3 memberedalicyclic cycloolefin with a specific ruthenium catalyst. Cycloolefinring substituents are inert and do not adversely affect the chemical andthermal stability of the catalyst. WO 96/20235 describes thecorresponding polymerisation of dicyclopentadiene (DCPD) optionally withan at least 3 membered alicyclic cycloolefin. WO 96/16008 describes thecorresponding polymerisation of a bridged cycloolefin as a dimer, trimeror the like.

We have now surprisingly found that by selection of particular classesof novel and known polymerisable monofunctional monomers anddifunctional bridged monomers and combinations thereof, and polymerisingwith a class of transition metal catalyst, a novel type of product maybe obtained which exhibits excellent properties in terms of controllingcross-linking density, and associated product modulus and glasstransition temperature (Tg), allowing novel uses as elastomers, plasticsand composites. Particularly advantageous performance is obtained withuse of the known “Grubbs” catalysts.

In its broadest aspect the present invention provides a process for thecatalytic copolymerisation of strained (poly)cyclic olefins substitutedby at least one carbon skeletal group, wherein the olefins comprise amonofunctional monomer and a difunctional monomer.

Accordingly there is provided according to the present invention aprocess for the catalytic copolymerisation of strained activated cyclicolefins comprising contacting a strained mono (poly)cyclic olefinmonomer of formula

with at least 1 wt % of a strained di (poly)cyclic olefin monomer offormula

in the presence of a catalyst or an initiating agent wherein the group

represents a strained (poly)cyclic olefin, tail Y and spacer X comprisepreferably electron withdrawing and property modulating groups

whereby the monomers form a copolymer comprising the repeating unit

and at least 1 wt % of the unit

which is adapted for subsequent cross linking of respective copolymerchains in the presence of heat and catalyst to form an amount of a crosslinked copolymer comprising the unit,

wherein groups are as hereinbefore defined.

The process of the invention provides for preparation of polymericmaterials having tailored properties, whereby monofunctional monomertail Y and difunctional monomer spacer X may be selected to have desiredproperties in terms of stiffness or flexibility, mobility or immobility,in terms of tail or spacer length. spatial orientation, and may becombined in any given ratio of monomers and the like.

Without being limited to this theory it is thought that the strained(poly)cyclic olefins of the invention may in fact be substituted by anynature of substituent which allows variation in “softness” and“hardness” or the like and regulation of crosslinking of polymericmaterial. The most convenient form allowing gradation of properties isthat of a carbon skeleton which may be varied in length. The substituentaccording to the invention is also normally linked to the olefin by anelectron withdrawing group, for reasons of ease of synthesis and thelike. Other linking groups may be envisaged such as simple hydrocarbon,phenyl, or alkoxyl (electron donating), whereby the process of theinvention may however be carried out with use of any combination of monoand difunctional monomer as hereinafter defined

Reference herein to a monofunctional monomer, hereinafter CnM, and adifunctional monomer, hereinafter CmD, is to compounds comprisingrespectively one and two strained (poly)cyclic olefin functional units.

The cyclic olefin is preferably a monocyclic olefin, more preferablynorbornene, substituted in the 5 and/or 6 positions by exo- and/orendo-normally electron withdrawing group(s) and property modulating tailY and spacer X as hereinbefore defined.

Preferably an electron withdrawing group is a carbonyl group.

Preferably the monofunctional and difunctional monomer are of formulae Iand II:

wherein at least one R¹ is a group Y and comprises a preferably electronwithdrawing group, facilitating ROMP reaction with monomer II, and Xcomprises a 2, 3 or 4-valent or two 2-valent optionally substitutedhydrocarbon spacer group(s) adapted to bridge adjacent crosslinkedchains and which provides for controllable uniformity and degree ofcross linking, providing controlled modulus and Tg.

Preferably at least one R¹ is independently selected from COOR², CONR²,COR²and the like

in which R² is selected from straight chain and branched, saturated andunsaturated C₁₋₁₂ hydrocarbon optionally substituted by one or morehydroxy, halo, aryl, cyclo C₁₋₈ alkyl, bisphenol such as bisphenol A,bisphenol F, phenol, hydroquinone and the like, and optionally includingat least one heteroatom such as O, P;

and one or more of the remaining groups R¹ may be selected from H, C₁₋₃alkyl, halo such as F and the like;

or two groups R¹ together form a cyclic amide or anhydride —(CH₂)_(p)CONR³CO—; —(CH₂)_(p) COOCO—

in which p is 0-4, and is 0 when the two groups form a fused structureor 1-4 when the two groups form a spiro structure;

R³ is as hereinbefore defined for R² and is a bridging unit; and

X is a linear or fused bridging moiety as hereinbefore defined.

Preferably X is a linear bridging group —COOR²COO— wherein R² is ashereinbefore defined, substituting the cyclic olefin at the 5 positionsand the 6 positions are unsubstituted or substituted by H, C₁₋₃ alkyl,halo such as F and the like; or

X is a fused bridging group —(CO)₂NR³N(CO)₂— in which —(CO)₂ N forms a 5membered cyclic ring with the 5 and 6 positions of each cyclic olefin,

and wherein R³ is as hereinbefore defined.

Monomers may be exo-, endo- or a mixture thereof. The process of theinvention allows the option to select isomers for desired Tg (endo isstiffer than exo) and % trans isomer in the product. Preferably monomersare exo-, which are generally more reactive, than endo- althoughresulting in lower product Tg.

Preferably the process comprises dissolving the difunctional monomer inthe monofunctional monomer and adding initiator in monomer solution. Theprocess conditions may be controlled by selection of monomer ratio andisomer type to provide well ordered living polymerisation or otherwise.It is a particular advantage that the process provides substantiallycomplete cure.

The process of the invention provides as polymeric product of thereaction of I and II a crosslinked structure, an example of which isillustrated in FIG. 1, in which the nature (length) of R leads tocontrol of properties within the system from soft thermoset elastomersto hard or rigid thermoset materials.

The polymerisation is suitably carried out in a predetermined ratio ofI:II determining cross-link density and Tg. The selection of groups R²,R³ and X as appropriate determines the material as hard or soft and itsmodulus and Tg.

A preferred ratio of monomer to difunctional monomer I:II is in therange 99:1 to 50:50, preferably 95:5 to 70:30 or 99:1 to 90:10, whichmay conveniently be expressed as CnM+x% CmD. More preferably x is 1, 2,2.5, 3, 5, 8, 10, 30 etc, and is preferably 1 for homogeneous cure.

Contacting the monomer of formula II as hereinbefore defined ispreferably in the presence of a catalyst comprising the reaction productof a metal oxide or halide and an alkylating agent. Preferred metals areselected from metals of Group VIII of the Periodic Table of the ElementsMo, Ru, Os, Ir, Rh and Re. Preferred is the “Grubbs” catalyst. Thecatalyst may be as described in WO 97/38036, WO 96/20235 or WO 96/16008as hereinbefore referred, the contents of which are incorporated hereinby reference.

In some instances it is however possible to use the commercially knownair sensitive catalyst comprising a Molybdate initiator (BFGoodrich) andstill obtain the advantages of the novel polymerisation process andproducts.

Traditional ring opening metathesis catalysts comprising a metal oxideMXn and cocatalyst such as R₃Al or EtAlCl₂ in combination, optionallywith an O-containing promoter such as EtOH or PhOH may also be employed,depending on selection of cyclic olefin substituent.

The catalyst may be in the presence of or include additional catalyticcomponents or catalytic supports. Reaction may be in a suitable inertatmosphere according to choice of catalyst. The catalyst is present incatalytically effective amount, for example in an amount of 10,000:1 eg4,000:1 monomer:catalyst.

The polymerisation reaction is suitably carried out in substantialabsence of any added solvents, the components being mutually compatible.The reaction is carried out at elevated temperature preferably in excessof room temperature up to approximately 200° C. preferably in the rangeof 60° C.-140° C. or 160° C.-200° C., depending on preferred Tg, eg 90°C.-100° C. to give homogeneous cure. Curing is carried out for asuitable period for example approximately 1 hour. Degassing of monomersis preferably carried out prior to reaction, which may be carried outwithout need for atmosphere control, or may be carried out in an inertatmosphere, depending on choice of catalyst.

The process of the invention is preferably suited for the preparation ofelastomers, plastics, composites in any desired form as shaped products,films, coatings and the like. It is a particular advantage of theprocess of the invention that such compounds may be readily prepared inwhich polymerisable monofunctional monomers and/or difunctional bridgedmonomers are selected to allow controlled crosslinking. The processtherefore provides a known and a novel route to access whole ranges ofnew products using known and novel polymerisable monofunctional monomersand/or difunctional bridged monomers.

In a further aspect of the invention there is provided a class of novelmonofunctional monomers of the formula Ii as hereinbefore defined forformula I except that when two R¹ together form a cyclic amide, R³ isalkyl having 3 or more carbon atoms, but is not phenyl.

In a further aspect of the invention there is provided a class of noveldifunctional bridged monomers of the formula IIi as hereinbefore definedfor formula II.

Compounds of the formula I, Ii, II and IIi as hereinbefore defined maybe obtained commercially or prepared by known means using Diels Aldermethodology.

Copolymers may be exo- or endo- or mixtures thereof and are preferablysubstantially all exo- as hereinbefore described.

Using this methodology compounds of formula I are obtained from reactionof CPD or a precursor thereof (DCPD may be used and cracks in situ atelevated temperature to yield CPD) with a compound of formula IV:

or of DCPD with a compound of formula V or VI

to yield the fused cyclic or spiro dianhydride (VII) and conversion withR³NH₂ to 5,5′ or 5,6 cyclo substituted products of formula I

Intermediate compounds of formula IV as hereinbefore defined may beobtained commercially or by known methodology.

Compounds of formula II may be obtained by analogy with thecorresponding compound of formula I by reaction of CPD with a compoundof formula VIII

to yield the linear bridged monomer or reaction of the fuseddicarboxyanhydride VII above with diamine H₂N(CH₂)₀₋₁₂NH₂ to yield thefused bridged dicarboxyimide monomer.

Compounds of formula I as hereinbefore defined comprising a poly (1 to10) cyclic olefin are obtained by interconversion from the correspondingcompound of formula I comprising a monocyclic olefin by Diels Alderreaction with CPD

In a further aspect of the invention there is provided a process for thepolymerisation of polymerisable monofunctional monomers of formula (Ii)as hereinbefore defined.

In a further aspect of the invention there is provided a method forselecting a mono and difunctional monomer as hereinbefore defined,comprising determining modulus and chemical properties of desiredcross-links, selecting a ratio of mono:di functional monomersdetermining the degree of cross-linking, for the cross-linkingcopolymerisation reaction thereof to provide product with desiredproperties. The present invention provides choice of multiplicity andnature of polymerisable components to control properties of product inthe range of thermoplast (polymerisation of Ii or of IIi) throughthermoset (copolymerisation of I and II). Selection of substituents andcontrol of monomer molecular weight allow control of malodourousvolatiles during the process and from the polymerised product.

In a further aspect of the invention there is provided a method for thepreparation of shaped products comprising reaction injection molding(RIM) or resin transfer molding (RTM) using known techniques.

It is a particular advantage of the present invention that RTM may beemployed, by virtue of the lowered reactivity and slower rate ofreaction of the polymerisation process of the present invention, byvirtue of the presence of the functionalised cyclic olefin groups.

Accordingly the method comprises combining separate streams ofpolymerisable monofunctional monomers and/or difunctional bridgedmonomers and catalyst (RIM) or premixing (RTM), injecting into asuitable mold and simultaneously or subsequently heating to activateand/or complete the polymerisation reaction.

The method may employ any suitable reinforcement fibres and the like asknown in the art. In this case the mold suitably contains the fibrespreformed with use of a binder according to known techniques.

In a further aspect of the invention there is provided a shaped productobtained by the method.

Preferably the shaped product is suitable for any of the hereinbeforedefined uses and is associated with advantages in terms of properties(modulus, Tg) as hereinbefore defined.

In a further aspect of the invention there is provided a thermoset orthermoplast polymeric product obtained by a method as hereinbeforedefined.

The invention is now illustrated in non limiting manner with referenceto the following examples.

EXAMPLE 1 Synthesis of Monofunctional Monomers

The corresponding acrylate (1 mol) was dissolved in toluene and freshlyprepared CPD (1.2 mol) was added slowly at room temperature undernitrogen. The reaction mixture was then refluxed for 12 hours. Themonomer was recovered by removing volatiles under reduced pressure. Thestructure of the monomer was confirmed by ¹H and ¹³C nmr. The monomersare as shown in FIGS. 2, 3 and 4.

EXAMPLE 2 Synthesis of Difunctional Monomers

1. Bisphenol A diacrylyl ester: In a flange flask equipped with a highpower overhead mechanical stirrer, water condenser and a droppingfunnel, bisphenol A (1 mol) was dissolved in THF followed by theaddition of triethylamine (4 mol). The flask was kept at ice temperatureand under a slow stream of nitrogen. Acryloyl chloride (2 mol) was addeddropwise and the temperature was raised to room temperature. Thereaction mixture was then refluxed for 12 hours. The resulting mixturewas filtered and volatiles were removed under reduced pressure. Thecrude product was extracted with hot hexane and white crystallineproduct was obtained upon cooling the hexane solution. The structure ofthe monomer was confirmed by ¹H and ¹³C nmr and mass spectroscopy and isillustrated in FIG. 5.

2. Bisphenol A dinorbornenyl ester: Bisphenol A diacrylyl ester (1 mol)was dissolved in toluene and freshly prepared CPD (2.2 mol) was addedslowly at room temperature under nitrogen. The reaction mixture was thenrefluxed for 12 hours. The monomer was recovered by removing volatilesunder reduced pressure. The structure of the monomer was confirmed by ¹Hand ¹³C nmr and mass spectroscopy and is shown in FIG. 5.

EXAMPLE 3 Synthesis of Difunctional Monomers

Using the procedure for Bisphenol A diacrylyl ester above, but usinghydroquinone (1 mol), Hydroquinone diacrylyl ester was obtained. Thestructure of the monomer was confirmed by ¹H and ¹³C nmr and massspectroscopy and is shown in FIG. 6.

The monomer was converted to the difunctional monomer Hydroquinonedinorbornenyl ester using the above synthesis as shown in FIG. 6.

EXAMPLE 4 Synthesis of monofunctional monomers

Exo- and endo-Norbornene-5,6-dicarboxyanhydride (exo- and endo-M), andDicarboxyimide (exo-CnM (n=3,4,5,6, 7 and 8) and endo-C6M).

These monomers were synthesised and characterised using procedures asreferred and disclosed in Eur Polym J Vol 34, No 2 pp 153-157, 1998 andPolymer Vol 39, No 23, pp 5619-5625, 1998, Khosravi and Al-Hajaji andare illustrated in FIG. 7.

EXAMPLE 5 Synthesis of Difunctional Monomers

Exo- and endo-Dinorbornene-5,6-dicarboxyimide (exo-CnD, n=3,5,6,9,12).

Starting from the dicarboxyanhydride monomer of Example 4, the synthesisof these difunctional monomers is described as follows and illustratedin FIG. 7.

Synthesis and Characterisation of Difunctional Monomers

General Procedure for the Synthesis of exo,exo-Difunctional Monomers:exo-CnD

A known weight of exo-AN was dissolved in glacial acetic acid at118-120° C. in a round bottom flask equipped with a condenser, a solidsaddition tube (for solid diamines) or addition funnel (for liquiddiamines), a thermometer and a magnetic stirrer bar. The required amountof n-alkyl diamine was added slowly. The reaction mixture was refluxedfor 2 hours at 120° C. using a silicone oil bath. The reaction mixturewas poured into cold distilled water which was then extracted withdichloromethane. The organic layer was washed twice with distilledwater, dried over anhydrous magnesium sulphate, filtered and the solventwas removed under vacuum to give the difunctional monomers as whitepowders. Analytical samples were obtained by further recrystallisationfrom acetone.

Synthesis and Characterisation ofexo,exo-N,N′-Propylene-di-(norbornene-5,6-dicarboxyimides): (exo-C3D)

exo-AN (20.0 g, 0.12 mol) was dissolved in glacial acetic acid (130 ml)at 118-120° C. in a 3-necked round bottom flask equipped with acondenser, addition funnel, a thermometer and a magnetic stirrer bar.1,3-Diaminopropane (4.4 g, 5 ml, 0.06 mol) was added to the flask viathe dropping funnel over a period of 1 hour. The reaction mixture washeat to reflux for 2 hours, giving a pale yellow solution. The solutionwas poured into cold distilled water which was then extracted withdichloromethane. The organic layer was washed twice with distilledwater, dried over anhydrous magnesium sulphate, filtered and the solventwas removed under vacuum. The final product was obtained by furtherrecrystallisation from acetone to give the white powder, exo-C3D (40.0g, 0.11 mol, 91% yield).

Mpt: 131.6° C.; Elemental analysis—Found C, 68.78%, H, 5.98%, N, 7.73%;calculated for C₂₁H₂₂N₂O₄: C, 68.84%, H, 6.05%, N, 7.64%. ¹H nmr—(seeAppendix 2.33), (CDCl₃, 400 MHz), δ (ppm)): 6.28 (t, 4H, H_(2,3)), 3.46(t, 4H, H₈), 3.25 (p, 4H, H_(1,4)), 2.66 (d, 4H, H_(5,6)), 1.86 (p, 2H,H₉), 1.52 (m, 2H, H₇), 1.29 (m, 2H, H_(7′)). ¹³C nmr—(see Appendix2.34), (CDCl₃, 100 MHz), δ (ppm)): 177.94 (C_(10,11)), 137.82 (C_(2,3)),47.84 (C_(5,6)), 45.55 (C_(1,4)), 43.20 (C₇), 36.20 (C₈), 26.32 (C₉),Mass spectrum—(see Apendix 2.35), (EI⁺): 366 (C₂₁H₂₂N₄O₂, M⁺), 301(MH⁺−C₅H₆), 235 (MH⁺−C₁₀H₁₂), 66 (M⁺−C₁₆H₁₆N₄O₂). IR—(see Appendix2.36), (KBr disc, cm⁻¹): 3048 (olefinic C—H stretching), 2996-2881(saturated C—H stretching), 1859, 1776 (Asymmetric and symmetric C═Ostretching, respectively), 1425 (C—N stretching).

Synthesis and Characterisation ofexo,exo-N,N′-Pentylene-di-(norbornene-5,6-dicarboxyimides): (exo-C5D)

The same procedure as for the synthesis of exo-C3D was used tosynthesise exo-C5D, but the starting material in this case was1,5-diaminopentane (6.1 g, 0.06 mol) to yield exo-C5D as a white powder(42.5 g, 0.11 mol, 90% yield).

Mpt: 185.1° C.; Elemental analysis—Found C, 69.96%, H, 6.56%, N, 7.20%;calculated for C₂₃H₂₆N₂O₄: C, 70.03%, H, 6.64%, N, 7.10%. ¹H nmr—(seeAppendix 2.37), (CDCl₃, 400 MHz, δ (ppm)): 6.28 (t, 4H, H_(2,3)), 3.44(t, 4H, H₈), 3.26 (p, 4H, H_(1,4)), 2.67 (d, 4H, H_(5,6)), 1.57 (m, 4H,H₉), 1.51 (m, 2H, H₇), 1.21 (m, 2H, H₇), 1.31 (p, 2H, H₁₀). ¹³C nmr—(seeAppendix 2.38), (CDCl₃, 100 MHz), δ (ppm)): 178.05 (C_(11,12)), 137.80(C_(2,3)), 47.79 (C_(5,6)), 45.13 (C_(1,4)), 42.75 (C₇), 38.35 (C₈),27.26 (C₉), 24.30 (C₁₀). Mass spectrum—(see Appendix 2.39), (EI⁺): 394(C₂₃H₂₆N₄O₂, M⁺), 329 (MH⁺−C₅H₆), 263 (MH⁺−C₁₀H₁₂), 66 (M⁺−C₁₈H₂₀N₄O₂).IR—(see Appendix 2.40), (KBr disc, cm⁻¹): 3050 (olefinic C—Hstretching), 2999-2847 (saturated C—H stretching), 1858, 1777(Asymmetric and symmetric C═O stretching, respectively), 1420 (C—Nstretching).

Synthesis and Characterisation ofexo,exo-N,N′-Hexylene-di-(norbornene-5,6-dicarboxyimides): (exo-C6D)

The same procedure as for the synthesis of exo-C3D was used tosynthesise exo-C6D, but the starting material in this case was1,6-diaminohexane (7.0 g, 0.06 mol) to yield exo-C6D as a white powder(45.3 g, 0.11 mol, 92% yield).

Mpt: 154° C.; Elemental analysis—Found C, 70.13%, H, 6.84%, N, 6.84%;calculated for C₂₄H₂₈N₂O₄: C, 70.57%, H, 6.91%, N, 6.86%. ¹H nmr—(seeAppendix 2.41), (CDCl₃, 400 MHz, δ (ppm)): 6.27 (t, 4H, H_(2,3)), 3.43(t, 4H, H₈), 3.26 (p, 4H, H_(1,4)), 2.66 (d, 4H, H_(5,6)), 1.52 (m, 6H,H₉, and H₇), 1.31 (m, 4H, H₁₀), 1.20 (m, 2H, H_(7′)). ¹³C nmr—(seeAppendix 2.42), (CDCl₃, 100 MHz, δ (ppm)): 177.94 (C_(11,12)), 137.67(C_(2,3)), 47.66 (C_(5,6)), 45.01 (C_(1,4)), 42.62 (C₇), 38.40 (C₈),27.45 (C₉), 26.33 (C₁₀). Mass spectrum—(see Apendix 2.43), (EI⁺): 408(C₂₄H₂₈N₄O₂, M⁺), 343 (MH⁺−C₅H₆), 277 (MH⁺−C₁₀H₁₂), 66 (M⁺−C₁₉H₂₂N₄O₂).IR—(see Appendix 2.44), (KBr disc, cm⁻¹): 3050 (olefinic C—Hstretching), 2999-2889 (saturated C—H stretching), 1860, 1777(Asymmetric and symmetric C═O stretching, respectively), 1420 (C—Nstretching).

Synthesis and Characterisation ofexo,exo-N,N′-Nonylene-di-(norbornene-5,6-dicarboxyimides): (exo-C9D)

The same procedure as for the synthesis of exo-C3D was used tosynthesise exo-C9D, but the starting material in this case was1,9-diaminononane (9.5 g, 0.06 mol) to yield exo-C9D as a white powder(44.7 g, 0.10 mol, 83% yield).

Mpt: 68° C.; Elemental analysis—Found C, 71.82%, H, 7.99%, N, 6.23%;calculated for C₂₇H₃₄N₂O₄: C, 71.97%, H, 7.61%, N, 6.22%. ¹H nmr—(seeAppendix 2.45), (CDCl₃, 400 MHz, δ (ppm)): 6.28 (t, 4H, H_(2,3)), 3.43(t, 4H, H₈), 3.26 (p, 4H, H_(1,4)), 2.66 (d, 4H, H_(5,6)), 1.52 (m, 6H,H₉ and H₇), 1.25 (m, 12H, H₁₀₋₁₂ and H_(7′)). ¹³C nmr—(see Appendix2.46), (CDCl₃, 100 MHz, δ (ppm)): 178.07 (C_(13,14)), 137.78 (C_(2,3)),47.75 (C_(5,6)), 45.11 (C_(1,4)), 42.68 (C₇), 38.67 (C₈), 29.19 (C₉),27.00 (C₁₀), 27.69 (C₁₁), 26.84 (C₁₂). Mass spectrum—(see Appendix2.47), (EI⁺): 450 (C₂₇H₃₄N₄O₂, M⁺), 385 (MH⁺−C₅H₆), 319 (MH⁺−C₁₀ H₁₂),66 (M⁺−C₂₂H₂₈N₄O₂).

IR—(see Appendix 2.48), (KBr disc, cm⁻¹): 3050 (olefinic C—Hstretching), 2997‥2880 (saturated C—H stretching), 1860, 1779(Asymmetric and symmetric C═O stretching, respectively), 1427 (C—Nstretching).

Synthesis and Characterisation ofexo,exo-N,N′-Dodecylene-di-(norbornene-5,6-dicarboxyimides): (exo-C12D)

The same procedure as for the synthesis of exo-C3D was used tosynthesise exo-C12D, but the starting material in this case was1,12-diaminododecane (12.0 g, 0.06 mol) to yield exo-C12D as a whitepowder (47.1 g, 0.10 mol, 80% yield).

Mpt: 64° C.; Elemental analysis—Found C, 73.29%, H, 8.51%, N, 5.79%;calculated for C₃₀H₄₀N₂O₄: C, 73.14%, H, 8.18%, N, 5.69%. ¹H nmr—(seeAppendix 2.49), (CDCl₃, 400 MHz, δ (ppm)): 6.28 (t, 4H, H_(2,3)), 3.46(t, 4H, H₈), 3.27 (p, 4H, H_(1,4)), 2.66 (d, 4H, H_(5,6)), 1.44 (m, 6H,H₉ and H₇), 1.24 (m, 18H, H₁₀₋₁₃ and H_(7′)). ¹³C nmr—(see Appendix2.50), (CDCl₃, 100 MHz, δ (ppm)): 178.35 (C_(14,15)), 138.06 (C_(2,3)),48.02 (C_(5,6)), 45.39 C_(1,4)), 42.94 (C₇), 38.99 (C₈), 29.70 (C₉),29.66 (C₁₀), 29.37 (C₁₁), 28.01 (C₁₂), 27.19 (C₁₃). Mass spectrum—(seeAppendix 2.51), (EI⁺): 492 (C₃₀H₄₀N₄O₂, M⁺), 427 (MH⁺−C₅H₆), 361(MH⁺−C₁₀H₁₂), 66 (M⁺−C₂₅H₃₄N₄O₂). IR—(see Appendix 2.52), (KBr disc,cm⁻¹): 3045 (olefinic C—H stretching), 2997-2879 (saturated C—Hstretching), 1860, 1779 (Asymmetric and symmetric C═O stretching,respectively), 1424 (C—N stretching).

Other monomers are shown in FIGS. 8 and 9.

EXAMPLE 6 Polymerisation of Monofunctional Monomer

Polymer of N-Hexylnorbornene-5,6-dicarboxyimide exo-C6M;

The monomer (20 g , 0.08 mol) and ruthenium carbene initiator (17 mg,2.1×10-5 mol, ratio [monomer]:[initiator] 3,900:1) were mixed in a smallreaction vessel and stirred at room temperature for 15 minutes. After 15minutes, the reacting mixture was introduced into a glass mould using asyringe. The filled mould was placed in an oven at 60C for 20 minutesand 160C for 60 minutes. The mould then was removed from the oven andthe final product was removed and allowed to cool to room temperature.The product is a glassy polymer, the extent of polymerisation is 98% (ie2% residual monomer).

EXAMPLE 7 Polymerisation of Monofunctional Monomer

Using the same procedure as Example 6 the polymer of norborneneisobornyl carboxylate was obtained as illustrated in FIG. 10.

EXAMPLE 8 Copolymerisation of Monofunctional and Difunctional Monomers

Using the same procedure as Example 6 with a mixture of neat monomersexo-CnM; n=2,3,4,5,7 and difunctional monomer exo-CnD; n=3,5,6,9,12 ofExample 4 and FIG. 7 above, and initiator, thermoset polymer wasobtained.

EXAMPLE A1 Testing of Copolymer Samples C5M M/I 8.000 and C12D

Samples obtained from Example 8 were subject to tests to measure Tg andmodulus as a function of incomplete/complete cure, homogeneity of cure,crosslinker and absolute values as a function of amount of crosslinkerpresent.

The results are shown in FIG. 11 for samples prepared from C5M +1%,2.5%, 10% C12D.

FIG. 11 illustrates:

a) sharp Tg transition, indicating there is no inhomogeneous cure attemperature above or below Tg;

b) very flat plateau modulus above Tg;

c) plateau modulus increases with increasing percentage of cross-linker;

d) Tg shifts up with increasing percentage of crosslinker: height oftransition decreases with increasing % of crosslinker, indicatinggenuine and complete crosslinking is present.

Further advantages of the invention are apparent from the foregoing.

What is claimed is:
 1. A process for the catalytic copolymerisation ofstrained activated cyclic olefins consisting of contacting 99-50 partsof an activated strained mono (poly)cyclic olefin monofunctional monomerof formula

with 1-50 parts of a strained di(poly)cyclic olefin difunctional monomerof formula

in the presence of a catalyst or an initiating agent, wherein the amountof mono and difunctional monomers totals 100 parts of monomer whereinthe group

represents a strained (poly)cyclic olefin, whereby the monomers form acopolymer comprising the repeating unit

and 1-50 parts of the unit

which is adapted for subsequent cross linking of respective copolymerchains in the presence of heat and catalyst to form an amount of a crosslinked copolymer comprising the unit,

wherein the monofunctional and difunctional monomer are of formulae Iand II:

wherein at least one R¹ is a group Y facilitating non-DCP ROMP reactionwith monomer II, and X comprises a 2, 3 or 4-valent or two 2-valentoptionally substituted hydrocarbon spacer group(s) adapted to bridgeadjacent crosslinked chains and which provides for controllableuniformity and degree of cross linking, providing controlled modulus andTg wherein at least one R¹ is independently selected from COOR², CONR²and COR²; in which R² is selected from straight chain and branched,saturated and unsaturated C₁₋₁₂ hydrocarbon optionally substituted byone or more hydroxy, halo, aryl, cyclo C₁₋₈ alkyl, bisphenol, phenol,hydroquinone, and optionally including at least one heteroatom; and oneor more of the remaining groups R¹ is selected from H, C₁₋₃ alkyl andhalo; or two groups R¹ together form a cyclic amide or anhydride—(CH₂)_(p) CONR³CO—; —(CH₂)_(p) COOCO— in which p is 0-4, and is 0 whenthe two groups form a fused structure or 1-4 when the two groups form aspiro structure; R³ is as hereinbefore defined for R² and is a bridgingunit; and wherein X is a linear bridging group —COOR²COO— wherein R² isas hereinbefore defined, substituting the cyclic olefin at the 5positions and the 6 positions are unsubstituted or substituted by asubstituent selected from H, C₁₋₃ alkyl and halo; or X is a fusedbridging group —(CO)₂NR³N(CO)₂— in which —(CO)₂ N forms a 5 memberedcyclic ring with the 5 and/or 6 positions of each cyclic olefin, or amethylene group

 and wherein R³ is as hereinbefore defined.
 2. The process as claimed inclaim 1 wherein the monofunctional monomers, the difunctional monomers,or both are exo-.
 3. The process as claimed in claim 1 which comprisesdissolving the difunctional monomer in the monofunctional monomer in theabsence of an added solvent and adding initiator to the mixture of neatmonomers in the absence of the added solvent.
 4. The process as claimedin claim 1 wherein ratio of the monofunctional monomer to thedifunctional monomer I:II is in the range 99:1 to 50:50.
 5. The processas claimed in claim 1 wherein catalyst comprises the reaction product ofa metal oxide or halide and an alkylating agent.
 6. The process asclaimed in claim 1 wherein the catalyst comprises well defined rutheniumcarbene initiator.
 7. The process as claimed in claim 1 which is carriedout at elevated temperature in excess of room temperature up to 200° C.depending on preferred Tg, to give homogeneous cure.
 8. The process asclaimed in claim 1 for the preparation of elastomers, plastics,composites in any desired form as shaped products, films, coatings andthe like.
 9. The process as claimed in claim 1 including additionallyselecting the mono and difunctional monomer for polymerisation,comprising determining modulus and chemical properties of desiredcross-links, selecting a ratio of mono:di functional monomersdetermining the degree of cross-linking, for the cross-linkingcopolymerisation reaction thereof to provide product with desiredproperties.
 10. The process as claimed in claim 12 includingadditionally selecting the mono and difunctional monomer forpolymerisation, comprising determining modulus and chemical propertiesof desired cross-links, selecting a ratio of mono:di functional monomersdetermining the degree of cross-linking, for the cross-linkingcopolymerisation reaction thereof to provide product with desiredproperties.
 11. A method for the preparation of shaped products whichcomprises conducting the process of claim 1 for reaction injectionmolding (RIM) or resin transfer molding (RTM), by combining separatestreams of the polymerisable monofunctional monomers and/or difunctionalbridged monomers and catalyst (RIM) or premixing (RTM), injecting into asuitable mold and simultaneously or subsequently heating to activateand/or complete the polymerisation reaction.
 12. A thermoset orthermoplast polymeric product or a shaped product obtained by theprocess of claim 1.